Heterogeneous photo-Fenton degradation of phenolic aqueous solutions over iron-containing SBA-15 catalyst

A novel iron-containing mesostructured material has been successfully tested for the heterogeneous photo-Fenton degradation of phenolic aqueous solutions using near UV–vis irradiation (higher than 313 nm) at room temperature and close to neutral pH. This catalyst is a composite material that contains crystalline hematite particles embedded into the mesostructured SBA-15 matrix in a wide distribution of size (30–300 nm) and well dispersed ionic iron species within the siliceous framework. The outstanding physico-chemical properties make this material a promising photocatalyst leading to better activity than other unsupported iron oxides. An experimental design model has been applied to assign the weight of catalyst and hydrogen peroxide concentrations in the photo-Fenton processes over this particular material. The catalytic performance has been monitored in terms of aromatics and total organic carbon (TOC) conversions, whereas the catalyst stability was evaluated according to the metal leached into the aqueous solution. Hydrogen peroxide concentration plays an important role in the stability of the iron species, preventing their leaching out into the solution, in contrast to the effect shown in typical dark-Fenton reaction. The homogeneous leached iron species result in very little contribution to the overall photocatalytic process. Catalyst loadings of 0.5 g/L and concentration of hydrogen peroxide close to the stoichiometric amount have yielded a total abatement of phenol and a remarkable organic mineralization.     

Oxidative dehydrogenation of ethane with carbon dioxide over silica molecular sieves supported chromium oxides:Pore size effect

SBA-15 with varied pore size from 4 to 8 nm were synthesized by tuning the temperature of hydrothermal treat-ment,the supports were then used to load the active phase CrOx through a conventional impregnation method.The resulting catalysts were characterized by small/wide angle XRD,N2 adsorption/desorption,FT-IR,TEM-EDX,XPS,TPR and CO2-TPD to study the feature of structure,surface chemical state,redox and basicity.It was found from these results that the metal species could be well dispersed on catalysts with larger pore size.Cr6+species could enter into the framework by substituting the Si atoms of SBA-15,and Cr3+mainly exist on extra frame-work Pore size had profound effects on reducibility,surface composition and basicity.Cr6+species were neces-sary to activate the C-H bonds of alkanes,while the basicity played an important role in activating C-O bonds of CO2.The best performances were achieved over the sample Cr supported on SBA-15 with a pore diameter of 7 nm in oxidative dehydrogenation of ethane in the presence of CO2.     

Use of different mesostructured materials based on silica as cobalt supports for the Fischer–Tropsch synthesis

To obtain a novel, active and selective to diesel catalytic material for syngas processing via Fischer–Tropsch synthesis (FTS), a series of 20 wt.% cobalt catalysts has been prepared by impregnation of a mesoporous molecular sieve based on silica (SBA-15, Al-MCM-41, INT-MM1), and a commercial amorphous silica for comparison purposes. All materials were characterized by several physico-chemical techniques: AAS, BET surface area, XRD, TPR, and H₂ chemisorption with pulse reoxidation and finally their reactivity on the FTS reaction was evaluated at 523 K, 10 bar, and H₂/CO = 2. Catalytic and characterization results show a great influence of mesoporous support porosity on the structure, reducibility, and FTS catalytic behavior of cobalt oxide species supported over these ordered materials. It was found that the size of supported cobalt oxide species formed during the calcination step increased with the average pore size (D_p) of the mesoporous support. Thus, the catalyst with larger Co oxide species located in wide pore silica showed to be easily reducible, more active and very selective toward the diesel fraction. It seems to be the case of the Co/SBA-15 solid, which showed to be the most active solid (XCO 63%) when the same mass of catalyst was used. Under CO iso-conversion conditions (XCO 40%), Co/SBA-15 was more selective toward the formation of C₅₊ hydrocarbons (80%, α = 0.76) and less selective to CH₄ (15%). On the contrary, when Al-MCM-41 and INT-MM1 were used as supports, a lower selectivity to C₅₊ and CO conversion and higher CH₄ selectivity (20%) were observed due to the decrease of D_p, of the cobalt oxide species size and the reducibility degree of such species.     

Heterogeneous photo-Fenton oxidation of reactive azo dye solutions using iron exchanged zeolite as a catalyst

The heterogeneous photo-Fenton-type oxidation of reactive azo dye solutions has been investigated in a quartz batch reactor using artificial UVA as a light source. Fe-exchanged zeolite has been used as a heterogeneous catalyst in the process. The effect of various process variables on decolorization performance of the process was evaluated by examining temperature, pH, H₂O₂ dosage, catalyst loading, initial dye concentration and light intensity. The optimal operational parameters were found as follows: 35 °C, pH as solution pH 5.2, 15 mmol H₂O₂ dosage, 1 g/L catalyst loading. Stability and reuse of the catalyst were also tested. Mineralization and comparison with homogenous photo-Fenton process were evaluated by analyzing color removal and total organic carbon (TOC) values.     

Characterization and activity of copper and nickel catalysts for the oxidation of phenol aqueous solutions

Catalysts based on CuO/γ-alumina, CuAl₂O₄/γ-alumina, NiO/γ-alumina, NiAl₂O₄/γ-alumina and bulk CuAl₂O₄ have been structurally characterized by BET, porosimetry, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Their catalytic behaviors have also been tested for the oxidation of 5 g/l phenol aqueous solutions using a triphasic tubular reactor working in a trickle-bed regime and air with an oxygen partial pressure of 0.9 MPa at a temperature of 413 K. The copper and nickel catalysts supported on γ-alumina have surface areas of the same order as the support γ-alumina of ca. 190 m²/g and high active phase dispersions which were also confirmed by SEM, whereas the bulk copper aluminate spinel has a surface area of ca. 30 m²/g. XRD detects the phases present and shows a continuous loss of CuO by elution and the formation of a copper oxalate phase on the surface of the copper catalysts which also elutes with time. The NiO was also eluted but less than the copper catalysts. Only the copper and nickel spinel catalysts were stable throughout the reaction. Phenol conversion vs. time shows a continuous overall decrease in activity for the CuO/γ-alumina and NiO/γ-alumina catalysts. In turn, the copper and nickel spinel catalysts reach steady activity plateaus of 40 and 10%, respectively, of phenol conversion. The bulk copper aluminate spinel shows an activity plateau of 20% of the conversion which is lower than that from the copper aluminate/γ-alumina catalyst due to its lower surface area. Nickel catalysts always have lower activities than the copper catalysts for the phenol oxidation reaction. The copper catalysts drive a mechanism of partial phenol oxidation to carboxylic acids and quinone-related products with very high specific rates, and the nickel catalysts mainly drive a mechanism of CO₂ formation with lower conversion but with a potential higher catalyst life. The triphasic tubular reactor using trickle-bed regime largely avoids the mechanism of polymer formation as a catalyst deactivation process.     

Wet oxidation of phenol by hydrogen peroxide using heterogeneous catalysis Fe-ZSM-5: a promising catalyst

This letter presents an original approach to the treatment of phenolic aqueous wastes using H₂O₂ with heterogeneous catalysts. The experimental results indicate that the system using Fe-ZSM-5 zeolite with MFI structure is promising since it allows total elimination of phenol and significant total organic carbon (TOC) removal under mild working conditions. Moreover, Fe-ZSM-5 remains active after after successive runs. Compared with processes using homogeneous catalysis, the possibility of induced pollution caused by the metal ions in the solution is avoided.     

Cu-silicalite-1 catalyst for the wet hydrogen peroxide oxidation of phenol

The aim of the present work is to study the heterogeneous wet hydrogen peroxide catalytic oxidation (WHPCO) of phenol using copper bearing Silicalite-1 type zeolite, prepared by direct hydrothermal synthesis. The catalysts used for this study were three: one (Na)Cu-Silicalite-1 and two (H)Cu-Silicalite-1 prepared by different ion exchange methods. The results on catalytic activity for phenol abatement and hydrogen peroxide consumption of these materials are presented. The copper leaching during the reaction was evaluated for all samples. A comparison with the catalytic activity and stability of a Cu-Silicalite-1 material prepared by ionic exchange method is presented.     

Direct synthesis of phenol from benzene over hydroxyapatite catalysts

The direct synthesis of phenol from benzene in the gas phase was studied over hydroxyapatite catalysts. The reaction was carried out in a fixed-bed reactor at atmospheric pressure and reaction temperature of 450°C in the presence of ammonia. A high selectivity (about 97%) of phenol formation at about 3.5% conversion of benzene was achieved over catalysts containing Ca and Cu ions in the cation part of hydroxyapatite. Besides phenol as the main reaction product, aniline is also formed. The reaction mechanism involves formation of N₂O from NH₃ in the first step of reaction. Benzene is oxidized by active oxygen species which are formed on the catalyst by decomposition of N₂O.     

Mineralization of phenol by a heterogeneous ultrasound/Fe-SBA-15/H2O2 process: Multivariate study by factorial design of experiments

A novel heterogeneous catalyst has been used for the oxidation of aqueous solutions of phenol by catalytic wet peroxide oxidation assisted by ultrasound irradiation. This composite catalyst material that contains crystalline hematite particles embedded into a mesostructured SBA-15 matrix was used successfully in the oxidation of phenol by heterogeneous Fenton and photo-Fenton processes. Ultrasound is found to enhance the activity of the catalyst in the process, without prejudice to the stability of the iron supported species. The influence of different variables, such as hydrogen peroxide concentration or catalyst loadings in the reaction was studied by factorial design of experiments. Catalyst loadings of 0.6 g L⁻¹ and a concentration of hydrogen peroxide close to twice the stoichiometric amount yield a remarkable organic mineralization, accompanied by excellent catalyst stability. The coupled US/Fe-SBA-15/H₂O₂ process at room temperature is revealed as a promising technique for wastewater treatment.     

不同硅源合成介孔分子筛SBA-15的研究

采用两种不同硅源——硅酸钠（Na2SiO3·9H2O）和正硅酸四乙酯（TEOS）合成介孔分子筛SBA-15。通过X射线粉末衍射（XRD）对样品进行表征，发现两种硅源合成的SBA-15都具有高度有序的二维六方立柱形结构。它们的比表面积相近，用TEOS作为硅源的SBA-15的孔容比用硅酸钠作为硅源的SBA-15的略大；用硅酸钠作为硅源的SBA-15有更高的微孔率和更厚的孔壁。以硅酸钠为硅源的SBA-15显示出分子自组装过程时间从24 h减少到3 h，并且对SBA-15模板性质没有有害影响。     

Catalytic aerobic oxidation of ethylbenzene over Co/SBA-15

Co(II)O was highly dispersed in the mesopores of SBA-15 by alcoholic impregnation method and characterized by XRD, TEM, UV–VIS DRS, TPR, and XRF techniques. It was found that tetrahedral coordinated Co(II)O was stabilized by SBA-15 at low Co-loading. Co/SBA-15 showed much higher activity than Co(OAc)₂ or Co₃O₄ in the liquid-phase aerobic oxidation of ethylbenzene under solvent-free condition.     

Microwave assisted selective oxidation of lignin model phenolic monomer over SBA-15

Microwave assisted oxidation of the lignin model monomer apocynol, 1-(4-hydroxy-3-methoxyphenoxy)-ethanol was carried out over mesoporous SBA-15 catalyst using H₂O₂ as oxidant to produce acetovanillone, vanillin and 2-methoxybenzoquinone. Reaction conditions were optimised in order to obtain acetovanillone selectively, which serves as a raw material for 3,4-dimethoxybenzoic acid, a building block for synthesis of the smooth muscle relaxant mebeverin. Under conventional heating reactions were sluggish and gave poor yields of a mixture of products. The use of increased amount of catalyst resulted in lowering of acetovanillone selectivity. The possibility of recycling the catalyst was also studied.     

Kinetics of the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation

In this study, high-gravity intensified heterogeneous catalytic ozonation is utilized for treatment of phenol-containing wastewater, and the kinetics of the direct reaction between ozone and phenol in the presence of excess tertiary butanol (TBA) is investigated. It is revealed that the direct reaction between ozone and phenol in the rotating packed bed (RPB) follows the pseudo-first-order kinetics with a reaction rate constant higher than that in the conventional bubbling reactor (BR). Under different conditions of temperature, initial pH, high-gravity factor, and gaseous ozone concentration, the apparent reaction rate constant varies in the range of 0.0160–0.115 min^-1. An empirical power-exponential model is established to characterize the effects of these parameters on the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation.     

粉煤灰负载Fe3+非均相光催化降解苯酚研究

利用粉煤灰负载Fe3+制备异相催化剂,研究了采用该催化剂的UV/Fenton体系对苯酚的降解效果,探讨了催化剂的制备方法对催化效率和稳定性的影响,并研究了反应体系、铁负载量、H2O2投加量和初始pH对苯酚降解效率的影响,考察了催化剂的重复利用性能.研究结果表明:由浸渍法制得的Fe-Al催化剂表现出了较好的稳定性及催化性能,在pH为3,H2O2投加量为5.0mmol/L,催化剂投加质最浓度为0.2 g/L的基准反应条件下,处理500mL初始质量浓度为100 mg/L的苯酚模拟废水,60 min之内对苯酚的降解率达95%以上,并且催化剂重复利用3次后,60 min内对苯酚的降解率仍可达93%以上.     

Catalytic wet oxidation of phenol over lanthanum strontium manganite

The catalytic performances of lanthanum strontium manganite (La_0.8Sr_0.2)Mn_0.98O₃, in catalytic wet oxidation (CWO) of a phenol solution under milder conditions of temperature (398–498 K) and pressure (P_o2=4 bar), in a batch reactor, have been investigated. Aim of this study is the evaluation of the effect of temperature, catalyst loading, phenol concentration and stirrer speed on phenol conversion. Experimental data obtained from the different test conditions are best-fitted to evaluate the effective reaction order and apparent activation energy.     

Catalytic property of Fe-Al pillared clay for Fenton oxidation of phenol by H2O2

Clay pillared with Fe-Al was synthesized as a catalyst for Fenton oxidation of phenol by hydrogen peroxide (H₂O₂). The pillaring process altered the basal space of clay, which is related to the amounts of aluminium and iron in the pillaring solution. The catalytic activity of the pillared clay was attributed to the accessible iron species, whose amount is regulated not only by the introduced iron species but also by the basal space that subsequently depends on the introduced aluminium species. The heterogeneous Fenton reaction exhibited an induction period followed by an apparent first order oxidation of phenol by H₂O₂. The induction period was proposed as an activation process of the surface iron species, which is thus enabled to complex with the reactants. The induction time (t_I) depended on temperature (T) and pH condition but irrelevant to the concentrations of phenol and H₂O₂ and the amount of catalyst. The rate of the oxidation process was evaluated with respect to the concentrations of phenol and H₂O₂, the amount of catalyst, pH and temperatures. During the catalytic reaction the trend of iron leaching showed an ascending period and a descending period, which was related to the presence of ferrous ions and ferric ions. The Fe-Al pillared was recovered through two procedures, dry powder and slurry, which have different effect on the induction period.     

Novel utilization of mesoporous molecular sieves as supports of cobalt catalysts in Fischer–Tropsch synthesis

Mesoporous molecular sieves (MCM-41 and SBA-15) with different pore diameters have been studied as supports of high loading of Co catalysts, and the performances in FT synthesis have been examined with a fixed bed stainless steel reactor at 2.0 MPa for the purpose of efficient production of C₁₀–C₂₀ fraction as the main component of diesel fuel. The method of exchanging template ions in uncalcined MCM-41 with Co²⁺ ions is effective for holding 10–20% Co within the mesopores while keeping the structure regularity of MCM-41 to some extent, compared with the conventional impregnation method using calcined MCM-41. At 523 K, CO conversion and selectivity to C₁₀–C₂₀ hydrocarbons are both higher at larger loading of 20% Co for the exchanged catalysts with pore diameters of 2.7–2.9 nm. When four kinds of 20% Co/SBA-15 with the diameters of 3.5–13 nm, prepared by the impregnation method using an ethanol solution of Co acetate, are used in FT synthesis at 523 K, the catalyst with the diameter of 8.3 nm shows the largest CO conversion, which is higher than those over MCM-41 supported Co catalysts. At a lower temperature of 503 K, however, the acetate-derived Co is almost inactive. In contrast, the use of Co nitrate alone or an equimolar mixture of the acetate and nitrate as Co precursor drastically enhances the reaction rate and consequently provides high space–time yield (260–270 g C/kg_cat h) of C₁₀–C₂₀ hydrocarbons. The X-ray diffraction and temperature-programmed reduction measurements show that the dependency of the catalytic performance of 20% Co/SBA-15 on its precursor originates probably from the differences in not only the reducibility of the calcined catalyst but also the dispersion of metallic Co. Catalyst characterization after FT synthesis strongly suggests the high stability of the most effective Co/SBA-15 in the dispersion and reducibility of the oxide species and in the mesoporous structure.     

Advances on the development of novel heterogeneous catalysts for transesterification of triglycerides in biodiesel

This paper describes experimental work done towards the search for more profitable and sustainable alternatives regarding biodiesel production, using heterogeneous catalysts instead of the conventional homogenous alkaline catalysts, such as NaOH, KOH or sodium methoxide, for the methanolysis reaction. This experimental work is a first stage on the development and optimization of new solid catalysts, able to produce biodiesel from vegetable oils. The heterogeneous catalytic process has many differences from the currently used in industry homogeneous process. The main advantage is that, it requires lower investment costs, since no need for separation steps of methanol/catalyst, biodiesel/catalyst and glycerine/catalyst. This work resulted in the selection of CaO and CaO modified with Li catalysts, which showed very good catalytic performances with high activity and stability. In fact FAME yields higher than 92% were observed in two consecutive reaction batches without expensive intermediate reactivation procedures. Therefore, those catalysts appear to be suitable for biodiesel production.     

Decolorization of reactive brilliant red X-3B by heterogeneous photo-Fenton reaction using an Fe–Ce bimetal catalyst

Decolorization of reactive brilliant red X-3B was studied by using an Fe–Ce oxide hydrate as the heterogeneous catalyst in the presence of H₂O₂ and UV. The decolorization rate was in the order of UV–Fe–Ce–H₂O₂ > UV–Fe³⁺–H₂O₂ > UV–H₂O₂ > UV–Fe–Ce ≥ Fe–Ce–H₂O₂ > Fe–Ce. Under the conditions of 34 mg l⁻¹ H₂O₂, 0.500 g l⁻¹ Fe–Ce, 36 W UV and pH 3.0, 100 mg l⁻¹ X-3B could be decolorized at efficiency of more than 99% within 30 min. The maximum dissolved Fe during the reaction was 1 mg l⁻¹. From the fact that the decolorization rate of the UV–Fe–Ce–H₂O₂ system was significantly higher than that of the UV–Fe³⁺–H₂O₂ system at Fe³⁺ = 1 mg l⁻¹, it is clear that the Fe–Ce functioned mainly as an efficient heterogeneous catalyst. UV–vis, its second derivative spectra, and ion chromatography (IC) were employed to investigate the degradation pathway. Fast degradation after adsorption of X-3B is the dominant mechanism in the heterogeneous catalytic oxidation system. The first degradation step is the breaking down of azo and CN bonds, resulting in the formation of the aniline- and phenol-like compounds. Then, the breaking down of the triazine structure occurred together with the transformation of naphthalene rings to multi-substituted benzene, and the cutting off of sulphonic groups from the naphthalene rings. The last step includes further decomposition of the aniline structure and partial mineralization of X-3B.